JP2000026601A5 - Poly-perfluoroalkyl-substituted polyamides as anti-fat agents for paper and foam stabilizers in aqueous fire-fighting foam - Google Patents
Poly-perfluoroalkyl-substituted polyamides as anti-fat agents for paper and foam stabilizers in aqueous fire-fighting foam Download PDFInfo
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- JP2000026601A5 JP2000026601A5 JP1999128008A JP12800899A JP2000026601A5 JP 2000026601 A5 JP2000026601 A5 JP 2000026601A5 JP 1999128008 A JP1999128008 A JP 1999128008A JP 12800899 A JP12800899 A JP 12800899A JP 2000026601 A5 JP2000026601 A5 JP 2000026601A5
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- 239000006260 foam Substances 0.000 title description 17
- 239000003795 chemical substances by application Substances 0.000 title description 3
- 239000004872 foam stabilizing agent Substances 0.000 title description 3
- 239000004952 Polyamide Substances 0.000 title description 2
- 229920002647 polyamide Polymers 0.000 title description 2
- 150000001875 compounds Chemical class 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- -1 perfluoroalkyl iodide Chemical compound 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 229920002873 Polyethylenimine Polymers 0.000 description 5
- 229920000768 polyamine Polymers 0.000 description 5
- 125000005336 allyloxy group Chemical group 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 125000004432 carbon atoms Chemical group C* 0.000 description 3
- GRWZHXKQBITJKP-UHFFFAOYSA-L dithionite(2-) Chemical compound [O-]S(=O)S([O-])=O GRWZHXKQBITJKP-UHFFFAOYSA-L 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 3
- 239000002798 polar solvent Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 2
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000005466 alkylenyl group Chemical group 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 150000002433 hydrophilic molecules Chemical class 0.000 description 2
- 125000005647 linker group Chemical group 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000003021 water soluble solvent Substances 0.000 description 2
- PNVPNXKRAUBJGW-UHFFFAOYSA-N (2-chloroacetyl) 2-chloroacetate Chemical compound ClCC(=O)OC(=O)CCl PNVPNXKRAUBJGW-UHFFFAOYSA-N 0.000 description 1
- LSWYGACWGAICNM-UHFFFAOYSA-N 2-(prop-2-enoxymethyl)oxirane Chemical compound C=CCOCC1CO1 LSWYGACWGAICNM-UHFFFAOYSA-N 0.000 description 1
- APRRQJCCBSJQOQ-UHFFFAOYSA-N 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid Chemical group OS(=O)(=O)C1=CC(O)=C2C(N)=CC(S(O)(=O)=O)=CC2=C1 APRRQJCCBSJQOQ-UHFFFAOYSA-N 0.000 description 1
- VXIVSQZSERGHQP-UHFFFAOYSA-N Chloroacetamide Chemical compound NC(=O)CCl VXIVSQZSERGHQP-UHFFFAOYSA-N 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N Chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N Diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- 101710019691 Olfr1 Proteins 0.000 description 1
- JVBXVOWTABLYPX-UHFFFAOYSA-L Sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 1
- RINCXYDBBGOEEQ-UHFFFAOYSA-N Succinic anhydride Chemical compound O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004429 atoms Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229940106681 chloroacetic acid Drugs 0.000 description 1
- 238000006704 dehydrohalogenation reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- CTKINSOISVBQLD-UHFFFAOYSA-N glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 229920001308 poly(aminoacid) Polymers 0.000 description 1
- 239000011528 polyamide (building material) Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N precursor Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing Effects 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
Description
【請求項11】 式CF3(CF2)h−I(ここで、hは、4〜18の整数である)のペルフルオロアルキルヨージドと、末端オレフィン性基を有する化合物との反応のための方法であって、
水溶性溶媒5〜40%を含む水性媒体中、かつペルフルオロアルキルヨージド1当量に基づいてジチオナイト0.02〜0.5当量の存在下に、0〜40℃の温度、7.0を超えるpHで、該反応を実施することを特徴とする方法。
11. A process for reacting a perfluoroalkyl iodide of the formula CF 3 (CF 2 ) h -I, wherein h is an integer from 4 to 18, with a compound having a terminal olefinic group. The method
In an aqueous medium containing 5 to 40% of a water-soluble solvent and in the presence of 0.02 to 0.5 equivalents of dithionite based on 1 equivalent of perfluoroalkyl iodide, a temperature of 0 to 40 ° C., a pH of more than 7.0 And carrying out the reaction.
【請求項13】 水性消火泡沫剤の泡安定性及び耐アルコール性を改善するための方法であって、
請求項1記載の化合物の有効量を、該泡沫剤に添加することを特徴とする方法。
13. A method for improving foam stability and alcohol resistance of an aqueous fire-fighting foam, comprising:
A method comprising adding an effective amount of the compound of claim 1 to said foam.
【請求項14】 水性消火泡沫剤の泡安定性及び耐アルコール性を改善するための方法であって、
請求項2記載の化合物の有効量を、該泡沫剤に添加することを特徴とする方法。
14. A method for improving foam stability and alcohol resistance of an aqueous fire-fighting foam, comprising:
3. A method comprising adding an effective amount of the compound of claim 2 to the foam.
【請求項15】 水性消火泡沫剤の泡安定性及び耐アルコール性を改善するための方法であって、
請求項4記載の化合物の有効量を、該泡沫剤に添加することを特徴とする方法。
15. A method for improving foam stability and alcohol resistance of an aqueous fire-fighting foam, comprising:
A method comprising adding an effective amount of the compound of claim 4 to said foam.
米国特許3,769,307は、ペルフルオロアルキル置換のポリエチレンイミン及びそれらの製造方法を請求している。この特許は、更に、撥油特性を与える新規な繊維仕上げ剤としてのそのような化合物の用途も請求している。ドイツ特許出願2018461は、ポリフルオロアルキル基の1個以上で置換されているポリエチレンイミン、並びに16個までのカルボキシ又はスルホン酸基及び/又は親水性アミド基を含むペルフルオロアルキル−置換ポリアミンである、ポリウレタンの界面活性剤及び泡安定剤を記載している。極性溶媒の消火泡のための泡安定剤化合物に向けられてはいないが、この特許の組成物は、アルコール/水混合物に非常によく溶解するが、アルコールにはほとんど溶解せず(=疎アルコール性)、水それ自身にも溶解せず、そのような泡安定剤のための候補である。実際、上記に引用したWO94/18245の参照は、テトラエチレンペンタミン、ペルフルオロアルキルアシルクロリド及びクロロ酢酸からのペルフルオロアルキル−及びカルボキシ−置換ポリエチレンイミンの合成を記載している。 U.S. Pat. No. 3,769,307 claims perfluoroalkyl-substituted polyethyleneimines and methods for their preparation. This patent further claims the use of such compounds as novel fiber finishes to provide oleophobic properties. DE-A-186 461 describes polyurethanes which are polyethyleneimines substituted with one or more of polyfluoroalkyl groups and perfluoroalkyl-substituted polyamines containing up to 16 carboxy or sulfonic acid groups and / or hydrophilic amide groups. Surfactants and foam stabilizers. Although not directed to foam stabilizer compounds for fire-extinguishing foam of polar solvents, the compositions of this patent dissolve very well in alcohol / water mixtures, but are poorly soluble in alcohol (= phophophobic) G), which does not dissolve in water itself, and is a candidate for such a foam stabilizer. Indeed, the reference of WO 94/18245 cited above describes the synthesis of perfluoroalkyl- and carboxy-substituted polyethyleneimines from tetraethylenepentamine , perfluoroalkylacyl chloride and chloroacetic acid.
極性溶媒の消火泡の泡安定剤として有用であり、複数のRF基並びにアミノ、カルボキシ又は他の親水性基を含むタイプのポリマー性RF−アミノ酸を含むポリマー性RF−アミンは、同様なルートにより、複数の第一級及び/又は第二級アミノ基、並びに複数の酸基を含むポリマーから、好都合にグリシジルエーテル(=AGE)との反応、続いてRF−ヨージドの付加及び部分脱ハロゲン化水素により、同様の高収率かつ実質的に廃棄物なしに製造することができることが見出されている。得られた、ポリ−ペルフルオロアルキル−アリルオキシ−及びポリ−ペルフルオロアルキル−ヨードプロピル−置換ポリアミノ酸の混合物は、紙の耐油脂剤として有用であるが、更に重要なことは、それらが極性溶媒の火災で用いられる水性消火泡(AFFF)配合物の優れた泡安定剤として働くことを見出したことである。 Are useful as foam stabilizers for fire fighting foam polar solvent, a plurality of R F group, as well as amino, type of polymeric containing a carboxy or other hydrophilic groups R F - polymers comprising the amino acid of R F - amine, like By a convenient route, from a polymer containing a plurality of primary and / or secondary amino groups , and a plurality of acid groups, a reaction with glycidyl ether (= AGE), followed by the addition of R F -iodide and a moiety It has been found that dehydrohalogenation allows for similar high yields and substantially waste-free production. The resulting mixture of poly-perfluoroalkyl-allyloxy- and poly-perfluoroalkyl-iodopropyl-substituted polyamino acids is useful as a grease-proofing agent for paper, but more importantly, they can be used in fires of polar solvents. It has been found that it works as an excellent foam stabilizer for the aqueous firefighting foam (AFFF) formulation used in E. coli.
ポリ−ペルフルオロアルキル−フルオロアリル−置換ポリアミノ酸であり、AR−AFFF剤の優れた泡安定剤である同様な化合物は、ポリエチレンイミンとペルフルオロアルキルエチルヨージドとの反応、続いてアミノ−反応性酸化合物、例えばクロロ酢酸又は無水コハク酸との反応により製造することができる。この反応は、ペルフルオロアルキルエチレン中間体を経由し、続いてHFの脱離により進行し、3−ペルフルオロアルキル−2−フルオロ−アリルアミン構造が得られると考えられている。ペルフルオロアルキルエチレンの第一級及び第二級アミンへの付加反応は、米国特許3,535,381及び4,853,141に記載されている。 A similar compound, which is a poly-perfluoroalkyl-fluoroallyl-substituted polyamino acid and an excellent foam stabilizer for AR-AFFF agents, is the reaction of polyethyleneimine with perfluoroalkylethyl iodide followed by amino-reactive acid It can be prepared by reaction with a compound such as chloroacetic acid or succinic anhydride. This reaction is believed to proceed via a perfluoroalkylethylene intermediate, followed by elimination of HF, resulting in a 3-perfluoroalkyl-2-fluoro-allylamine structure. Addition reactions of perfluoroalkyl ethylenes to primary and secondary amines are described in U.S. Patents 3,535,381 and 4,853,141.
の基であり、
Rは、水素又はメチルであり、
RFは、独立して、4〜20個の完全フルオロ化炭素原子を有する、直鎖若しくは分岐の、1価のペルフルオロ化アルキル若しくはアルケニル有機基であり、
RF′は、独立して、3〜19個の完全フルオロ化炭素原子を有する、直鎖若しくは分岐の、1価のペルフルオロ化アルキル若しくはアルケニル有機基であり、それぞれのRF及びRF′は、同一又は他のRF及びRF′とは異なり、
Xは、水素、−CH2CH(OH)CH2−O−CH2CH=CH2−又は−G−Yであり、
Gは、直接結合又は式−CH2−、−CH2CHR−、−CH2CH2C6H4−、−CH2CH2CH2−、−C6H4−、−CH(−COOH)CH2−、−CH2CH2CONHCH(OH)−、−COR1−、−CH2CHRCONHC(CH3)2(CH2)−(ここで、Rは、上記と同義である)若しくはそれらの混合物の結合基であり、
R1は、−CH=CH−、−CH2CH2−又は−C6H4−であり、
Yは、式−COOH、−SO3H、−PO3H2、若しくは−(PO3H)3Hの酸基、又はそれらの塩であるか、あるいは
−CONH2若しくは−CH(OH)CH2OH、又はそれらの基の混合物であり、
R2は、1〜20個の炭素原子を有するアルキル基、又は−CH2CH2CON(CH3)2、−CH2CH2CONHCH2OH、−CH2CH2CON(CH2OH)2、−CH2CH2N(R4)2、−CH2CR1−COOR4若しくは−CH2CH(OH)CH2−O−CH2CH=CH2、(ここで、R4は、炭素原子1〜18個を有するアルキル基であるか、又は−CH2CH2−OHである)であり、
R3は、R2と同義であるか、又は水素であり、そしてR1は、上記と同義である)
A−1のq単位、A−2のr単位、A−3のs単位及びA−4のt単位(ここで、q、r、s及びtは、ゼロ〜100の整数であり、かつq+r+s+tの合計は、5〜200であり、q+rの合計は、2に等しいか、又は2より大きく、そしてq+r/sの比は、0.1〜2である)を、ランダム分布で含む。
Is the basis of
R is hydrogen or methyl;
R F is independently a linear or branched, monovalent perfluorinated alkyl or alkenyl organic group having 4 to 20 fully fluorinated carbon atoms;
R F ′ is independently a linear or branched monovalent perfluorinated alkyl or alkenyl organic group having 3 to 19 fully fluorinated carbon atoms, each R F and R F ′ , Different from the same or other R F and R F ′,
X is hydrogen, —CH 2 CH (OH) CH 2 —O—CH 2 CH = CH 2 — or —G—Y,
G is a direct bond or the formula -CH 2 -, - CH 2 CHR -, - CH 2 CH 2 C 6 H 4 -, - CH 2 CH 2 CH 2 -, - C 6 H 4 -, - CH (-COOH ) CH 2 -, - CH 2 CH 2 CONHCH (OH) -, - COR 1 -, - CH 2 CHRCONHC (CH 3) 2 (CH 2) - ( wherein, R is as defined above) or their A linking group of a mixture of
R 1 is —CH = CH—, —CH 2 CH 2 — or —C 6 H 4 —,
Y has the formula -COOH, -SO 3 H, -PO 3 H 2, or - (PO 3 H) 3 H acid groups, or a salt thereof, or -CONH 2 or -CH (OH) CH 2 OH, or a mixture of those groups,
R 2 is an alkyl group having 1 to 20 carbon atoms, or —CH 2 CH 2 CON (CH 3 ) 2 , —CH 2 CH 2 CONHCH 2 OH, —CH 2 CH 2 CON (CH 2 OH) 2 , -CH 2 CH 2 N (R 4) 2, -CH 2 CR 1 -COOR 4 or -CH 2 CH (OH) CH 2 -O-CH 2 CH = CH 2, ( wherein, R 4 is carbon or an alkyl group having 1 to 18 atoms, a or -CH 2 CH 2 -OH),
R 3 is as defined for R 2 or hydrogen, and R 1 is as defined above.
Q unit of A-1, r unit of A-2, s unit of A-3 and t unit of A-4 (where q, r, s and t are integers from 0 to 100, and q + r + s + t Are from 5 to 200, the sum of q + r is equal to or greater than 2, and the ratio of q + r / s is from 0.1 to 2) in a random distribution.
本発明の新規なポリ−RF−(アリルオキシ/ヨードプロポキシ)ポリアミンは、まずアリルグリシジルエーテルを前駆体のポリアミンポリマーの第一級又は第二級アミノ基の部分と反応させ、次いでこのポリアリルオキシ−置換ポリアミノプレポリマーをアミノ−反応性有機若しくは無機酸性化合物又は他の親水性化合物と反応させ、次いでこの反応の生成物をペルフルオロアルキルヨージドと反応させることにより得られる。 The novel poly -R F of the present invention - (allyloxy / iodopropoxy) polyamines, first the allyl glycidyl ether is reacted with a primary or portion of the secondary amino groups of the polyamine polymer precursor, then the poly allyloxy -Obtained by reacting a substituted polyamino prepolymer with an amino-reactive organic or inorganic acidic compound or other hydrophilic compound and then reacting the product of this reaction with a perfluoroalkyl iodide.
有用なアミノ−反応性、非イオン性、親水性化合物は、オキシラン及びクロロアシルアミド、例えばグリシドール及びクロロアセトアミドである。 Useful amino-reactive, nonionic, hydrophilic compounds are oxiranes and chloroacylamides, such as glycidol and chloroacetamide.
反応媒体の塩基性特性のために、有機ヨウ化物の多くは、反応の間に脱離される。プレポリマーは、したがって、ヨードプロポキシ及びペルフルオロアルキル部分へのアリルオキシ結合基を有する混合物として得られる。有機ヨウ化物の完全な脱離が所望ならば、水酸化ナトリウム若しくはカリウムのような強無機塩基又は1,8−ジアザビシクロ〔5.4.0〕ウンデカ−7−エンのような強有機塩基の添加が必要である。 Due to the basic nature of the reaction medium, much of the organic iodide is eliminated during the reaction. The prepolymer is thus obtained as a mixture having allyloxy linking groups to the iodopropoxy and perfluoroalkyl moieties. If complete elimination of the organic iodide is desired, the addition of a strong inorganic base such as sodium or potassium hydroxide or a strong organic base such as 1,8-diazabicyclo [5.4.0] undec-7-ene. is necessary.
アリルオキシ基へのRF−Iの付加は、ナトリウムジチオナイトを用いて、0〜20℃の温度で実施することができる。Haung (Chin.J.Chem. 4, 350 and 358, (1990); Macromol Symp.82, 67, 1994) は、RF−Iに基づくジチオナイトの1当量の使用が、RF−Iの末端不飽和化合物への付加のために必要であることを教示している。意外にも、単に0.02〜0.5当量、好適には0.05〜0.2当量が、アリルオキシ−置換ポリアミドへの実質的に完全な付加を達成するに十分であることが見出された。この方法の利点は、着色が少なく、有機化学的に結合したヨウ素が多く保持されることである。更に、この方法は、より高い水性希釈で実施することができる。C1−C4アルコール、ジメチルホルムアミドのようなアミド又はケトンのような水溶性溶媒4〜10重量%を含む水性溶液中、0〜40℃で、RF−Iに基づいて、ジチオナイト0.02〜0.5当量、好適には0.05〜0.2当量の存在下に、末端二重結合へのRF−Iの付加を実施することは、したがって、本発明の別の目的である。 Addition of R F -I to allyloxy group, with sodium dithionite can be carried out at a temperature of 0 to 20 ° C.. Haung (Chin.J.Chem 4, 350 and 358 , (1990);. Macromol Symp.82, 67, 1994) , the use of 1 equivalent of dithionite based on R F -I is not end of R F -I It teaches what is needed for addition to saturated compounds. Surprisingly, it has been found that only 0.02 to 0.5 equivalents, preferably 0.05 to 0.2 equivalents, are sufficient to achieve substantially complete addition to the allyloxy-substituted polyamide. Was done. The advantage of this method is that it is less colored and retains more organically bound iodine. Further, the method can be performed at higher aqueous dilutions. C 1 -C 4 alcohol, an aqueous solution containing 4-10% by weight of a water-soluble solvent such as an amide or a ketone such as dimethylformamide, at 0 to 40 ° C., based on R F -I, dithionite 0.02 0.5 equivalents, preferably in the presence of 0.05 to 0.2 equivalents, to carry out the addition of the R F -I to terminal double bond, therefore, it is another object of the present invention .
有用なポリアミン出発材料は、約200〜10,000の範囲の数平均分子量を有する。それらは、典型的には、1:1:0〜1:2:1の範囲の比での4〜300の第一級、第二級及び第三級アミノ基を含むポリアルキレンイミンである。好適なものは、1,000〜5,000の分子量を有するポリエチレンイミンである。これらのポリアミン出発材料は、商業的に入手し得る。 Useful polyamine starting materials have a number average molecular weight in the range of about 200 to 10,000. They are typically polyalkylenimines containing 4-300 primary, secondary and tertiary amino groups in a ratio ranging from 1: 1: 0 to 1: 2: 1. Preferred is polyethylene imine having a molecular weight of 1,000 to 5,000. These polyamine starting materials are commercially available.
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US7011763B2 (en) * | 2001-11-27 | 2006-03-14 | Chemguard Incorporated | Fire extinguishing or retarding material |
US6951962B2 (en) * | 2002-04-12 | 2005-10-04 | Hercules Incorporated | Oil/grease- and water-sizing agent for treatment of cellulosics |
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